Radicals and anions: The TEMPO-mediated oxidation of magnesiated iodoarenes A provides highly regioregular poly(m-phenylenes) by strictly alternating anionic/radical cross-over chain-growth polymerization. Poly(m-phenylenes) with mean molecular weight (Mn) of up to 20 000 g mol-1 can be prepared under mild conditions by this method. The approach is a new concept for transition-metal-free polyarene synthesis. TEMPO=2,2,6,6-tetramethylpiperidine- N-oxyl radical. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.